JP6731125B2 - Selective poisoning of aromatization catalysts to enhance catalytic activity and selectivity - Google Patents

Description

The present disclosure relates to catalytic reforming processes and associated aromatization reactor vessels, and more particularly to the selection of aromatization catalysts containing transition metals and catalyst supports to enhance catalyst activity and selectivity. Regarding physical poisoning.

Catalytic conversion of non-aromatic hydrocarbons to aromatics, often referred to as aromatization or reforming, is an important industrial process that can be used to produce benzene, toluene, xylenes and the like. The aromatization or reforming process is often conducted in a reactor system that can contain one or more reactors containing transition metal based catalysts. These catalysts can provide increased selectivity of the desired aromatic compound and/or increased yield. However, under commercial reaction conditions, these catalysts slowly lose their activity, often with concomitant loss of selectivity for the desired aromatic compound. Such catalysts are often referred to as "spent" catalysts once the economic or operational thresholds have been exceeded.

Despite the presence of spent catalyst in the aromatization reactor, it was partly due to the costs associated with the unplanned outage as well as the cost of removing the spent catalyst and replacing it with new catalyst. Thus, it would be beneficial to keep the aromatization reactor running. Thus, the present disclosure is generally related to achieving these ends.

Methods for reforming hydrocarbons are disclosed and described herein. One such reforming method is to (a) provide a radial flow reactor comprising a catalyst bed, the catalyst bed comprising an outer reforming zone and an inner reforming zone, the outer reforming zone comprising: A second aroma comprising a spent first aromatization catalyst comprising a first transition metal and a first catalyst support, the inner reforming zone comprising a second transition metal and a second catalyst support. Providing an aromatization catalyst, and (b) introducing a catalyst poisoning agent into the radial flow reactor and contacting at least a portion of the spent first aromatization catalyst in the outer reforming zone. (C) introducing a hydrocarbon feed into a radial flow reactor containing the catalyst bed and contacting the hydrocarbon feed with the catalyst bed under reforming conditions to produce an aromatic product. , Can be included.

Another reforming method consistent with the present disclosure is to introduce a first hydrocarbon feed into a radial flow reactor containing (A) a catalyst bed and, under first reforming conditions, a first hydrocarbon feed. Contacting a feed with a catalyst bed to produce a first aromatic product, the catalyst bed including an outer reforming zone and an inner reforming zone, the outer reforming zone comprising: A first aromatization catalyst comprising a transition metal and a first catalyst support, and an inner reforming zone comprising a second aromatization catalyst comprising a second transition metal and a second catalyst support. , Performing step (A) for a period of time sufficient to produce and (B) form a spent first aromatization catalyst in the outer reforming zone, and (C) a radial flow. Introducing a catalyst poison to the reactor and contacting at least a portion of the spent first aromatization catalyst in the outer reforming zone; and (D) a second to the radial flow reactor containing the catalyst bed. Introducing a hydrocarbon feed of, and contacting the second hydrocarbon feed with a catalyst bed under second reforming conditions to produce a second aromatic product. You can

Also disclosed herein are aromatization reactor vessels and reactor systems. For example, an exemplary aromatization reactor vessel includes (i) a reactor wall, (ii) a catalyst bed positioned within the reactor vessel, (iii) a reactor wall and an outer particle barrier. A positioned outer annulus, the outer particle barrier and the outer annulus being connected to the outer annulus surrounding the catalyst bed, (iv) the reactor inlet for the feed stream, and (v) the central tube. A reactor outlet wherein the central tube is positioned within the reactor vessel and is surrounded by the catalyst bed. The catalyst bed can include an outer reforming zone and an inner reforming zone, the outer reforming zone including a deactivated first aroma including a first transition metal and a first catalyst support. The aromatization catalyst is included and the inner reforming zone includes a second aromatization catalyst including a second transition metal and a second catalyst support. The flow path for the feed stream begins at the reactor inlet, continues to the outer annulus, through the outer particle barrier, the outer reforming zone, and the inner reforming zone, to the central tube, and to the reactor outlet. be able to.

In these and other aspects of the invention, the first transition metal and the second transition metal may be the same or different. Similarly, the first catalyst support and the second catalyst support may be the same or different.

Both the foregoing summary and the following detailed description provide examples and are for illustration purposes only. Therefore, the above summary and the following detailed description should not be construed as limiting. Furthermore, features or variations may be provided in addition to those described herein. For example, an aspect can relate to various feature combinations and subcombinations described in the detailed description.
Note that any of the following [1] to [20] is one mode or one mode of the present invention.
[1]
A reforming method,
(A) introducing a first hydrocarbon feed into a radial flow reactor containing a catalyst bed and contacting the first hydrocarbon feed with the catalyst bed under first reforming conditions, Producing a first aromatic product, the method comprising:
The catalyst bed includes an outer reforming zone and an inner reforming zone,
The outer reforming zone comprises a first aromatization catalyst comprising a first transition metal and a first catalyst support,
Producing the inner reforming zone comprises a second aromatization catalyst comprising a second transition metal and a second catalyst support;
(B) performing step (A) for a period of time sufficient to form a spent first aromatization catalyst in the outer reforming zone;
(C) introducing a catalyst poisoning agent into the radial flow reactor and contacting with at least a portion of the spent first aromatization catalyst in the outer reforming zone;
(D) introducing a second hydrocarbon feed into the radial flow reactor containing the catalyst bed and contacting the second hydrocarbon feed with the catalyst bed under second reforming conditions. And producing a second aromatic product.
[2]
The first aromatization catalyst comprises about 0.3% to about 5% by weight of the first transition metal;
The method of [1], wherein the second aromatization catalyst comprises from about 0.3% to about 5% by weight of the second transition metal.
[3]
The first transition metal and the second transition metal include platinum,
The first catalyst carrier and the second catalyst carrier include K/L type zeolite and a binder containing alumina, silica, a mixed oxide thereof, or a mixture thereof;
The method according to [1], wherein the first aromatization catalyst and the second aromatization catalyst further contain chlorine and fluorine.
[4]
The first aromatic product and the second aromatic product independently comprise benzene, toluene, or a combination thereof,
The method of [1], wherein the first reforming condition and the second reforming condition independently comprise a reforming temperature in the range of about 350°C to about 600°C.
[5]
The method of [1], wherein the weight ratio of catalyst in the outer reforming zone to the inner reforming zone is in the range of about 1:1.5 to about 1:5.
[6]
The catalyst poisoning agent comprises a material configured to bind to the first transition metal such that the first transition metal does not catalyze an aromatization reaction and/or undergoes a decomposition reaction. The method according to [1], which does not catalyze.
[7]
The catalyst poisoning agent is from about 0.1:1 to about 0. 0, based on moles of the catalyst poisoning agent to moles of the first transition metal in the spent first aromatization catalyst. The method of [1], wherein the method is introduced at a molar ratio within the range of 75:1.
[8]
The method according to [1], wherein the aromatic yield of the used first aromatization catalyst after contact with the catalyst poisoning agent is less than 10% by weight.
[9]
The aromatic yield of the second aromatization catalyst is greater than the yield of the used first aromatization catalyst under the same test conditions,
The method of [1], wherein the aromatic selectivity of the second aromatization catalyst is greater than the selectivity of the spent first aromatization catalyst under the same test conditions.
[10]
The aromatic yield of the second aromatic product in step (D) is greater than the yield of the first aromatic product produced after step (B) and before step (C). The method described in [1] is also large.
[11]
The aromatic selectivity of the second aromatic product in step (D) is determined by the aromatic selectivity of the first aromatic product produced after step (B) and before step (C). The method according to [1], which is greater than sex.
[12]
A reforming method,
(A) providing a radial flow reactor comprising a catalyst bed, said catalyst bed comprising an outer reforming zone and an inner reforming zone,
The outer reforming zone comprises a spent first aromatization catalyst comprising a first transition metal and a first catalyst support,
Providing the inner reforming zone comprises a second aromatization catalyst comprising a second transition metal and a second catalyst support;
(B) introducing a catalyst poison into the radial flow reactor and contacting with at least a portion of the spent first aromatization catalyst in the outer reforming zone;
(C) introducing a hydrocarbon feed into the radial flow reactor containing the catalyst bed and contacting the hydrocarbon feed with the catalyst bed under reforming conditions to produce an aromatic product. And a method, including:
[13]
The aromatic yield of the aromatic product in step (c) is greater than the yield of aromatic product produced after step (a) and before step (b),
The aromatic selectivity of the aromatic product in step (c) is greater than the aromatic selectivity of the aromatic product produced after step (a) and before step (b) [12 ] The method of description.
[14]
An aromatization reactor vessel,
(I) a reactor wall,
(Ii) a catalyst bed positioned within the reactor vessel,
(Iii) an outer annulus positioned between the reactor wall and an outer particle barrier, the outer particle barrier and the outer annulus surrounding the catalyst bed;
(Iv) a reactor inlet for the feed stream,
(V) a reactor outlet connected to a central tube, the central tube being positioned within the reactor vessel and surrounded by the catalyst bed;
The catalyst bed includes an outer reforming zone and an inner reforming zone, the outer reforming zone including a deactivated first aromatization catalyst including a first transition metal and a first catalyst support. And wherein the inner reforming zone comprises a second aromatization catalyst comprising a second transition metal and a second catalyst support,
A flow path for the feed stream begins at the reactor inlet and continues to the outer annulus, through the outer particle barrier, the outer reforming zone, and the inner reforming zone to the central tube. , And an aromatization reactor vessel following the reactor outlet.
[15]
The aromatization reactor vessel is configured for catalytic conversion of non-aromatic hydrocarbons to aromatic hydrocarbons, including benzene, toluene, xylene, or combinations thereof,
The container according to [14], wherein the deactivated first aromatization catalyst is configured not to catalyze an aromatization reaction.
[16]
The first transition metal and the second transition metal include platinum,
The first catalyst carrier and the second catalyst carrier include K/L type zeolite and a binder containing alumina, silica, a mixed oxide thereof, or a mixture thereof;
The container of [14], wherein the deactivated first aromatization catalyst and the second aromatization catalyst further comprise chlorine and fluorine.
[17]
The weight ratio of catalyst in the outer reforming zone to the inner reforming zone is in the range of about 10:1 to about 1:10;
The amount of carbon on the deactivated first aromatization catalyst is in the range of about 1 wt% to about 10 wt %,
The container of [14], wherein the amount of carbon on the second aromatization catalyst is in the range of about 0.01 wt% to about 0.5 wt%.
[18]
The container of [14], wherein the aromatic yield of the deactivated first aromatization catalyst is less than 10 wt %.
[19]
The aromatization reactor vessel is configured as a radial flow reactor,
The central tube and the catalyst bed are concentrically positioned,
The vessel of [14], wherein the aromatization reactor is configured to reduce the temperature from the outer annulus to the central tube.
[20]
An aromatization reactor vessel system comprising 2 to 8 aromatization reactor vessels in series, at least one of which is the aromatization reactor vessel according to [14]. system.

The accompanying drawings, which are incorporated in and constitute a part of this disclosure, illustrate various aspects of the present invention. In the drawing:
FIG. 3 illustrates a partial cross-sectional view of an aromatization reactor vessel having an outer reforming zone and an inner reforming zone in an aspect of the invention. In another aspect of the invention, a reactor system containing a series of furnaces and reactor vessels is illustrated. FIG. 6 is a representative plot of reactor temperature as a function of location in the reactor from the outer annulus to the central tube when the catalyst closest to the outer annulus is spent catalyst. 3 is a representative plot of reactor temperature as a function of location in the reactor from the outer annulus to the central tube when the catalyst closest to the outer annulus is deactivated with catalyst poison. A plot of aromatic yield versus reaction time for the spent catalyst of Example 1 (closest to the outer annulus) and the spent catalyst of Example 2 (closest to the central tube) is presented. A plot of aromatic selectivity versus reaction time is presented for the spent catalyst of Example 1 (closest to the outer annulus) and the spent catalyst of Example 2 (closest to the central tube). A plot of aromatic yield versus reaction time for the catalyst bed of Example 3 (reference) and the catalyst bed of Example 4 (with deactivated or poisoned catalyst zones) is presented. Figure 3 presents a plot of aromatic selectivity versus reaction time for the catalyst bed of Example 3 (reference) and the catalyst bed of Example 4 (with deactivated or poisoned catalyst zones).

Definitions In order to more clearly define the terms used herein, the following definitions are provided. The following definitions apply to this disclosure, unless otherwise indicated. Where certain terms are used in this disclosure and are not specifically defined herein, unless the applicable definition conflicts with any other disclosure or definition applied herein. or unless in any claims unclear or impossible definition is applied, it may be applied definitions from ^{IUPAC Compendium of Chemical Terminology, 2 nd} Ed (1997). To the extent that any definition or use provided by any document incorporated herein by reference contradicts the definition or use provided herein, the definition or use provided herein has priority. To do.

Features of the subject matter are described herein so that different combinations of features may be recalled within particular aspects. For each and every aspect and feature disclosed herein, any combination that does not adversely affect the design, composition, process, or method described herein is a clear description of the particular combination. It is contemplated with or without. Moreover, unless explicitly stated otherwise, any aspect or feature disclosed herein may be combined to describe an inventive design, composition, process, or method consistent with the present disclosure. ..

Although apparatus, systems, and methods/processes are described herein in terms of “comprising” various components, devices, or steps, apparatus, systems, and methods/processes are also referred to otherwise. Unless stated otherwise, various components, devices, or steps may also “consist essentially of” or “consist of”.

The terms “a”, “an”, and “the” are intended to include plural forms thereof, eg, at least one. For example, disclosure of a "transition metal" or "catalyst poison" is meant to encompass a mixture or combination of one, or more than one transition metal or catalyst poison, unless otherwise stated. ..

"Spent" catalysts are generally referred to herein as catalyst activity, hydrocarbon feed conversion, desired product(s) yield, desired product(s) selectivity, or maximum operation. Although used to describe a catalyst that has unacceptable performance at one or more of its operating parameters, such as temperature or pressure drop across the reactor, the determination that a catalyst is "used" is one of these characteristics. Not limited to only. The unacceptable performance of the spent catalyst may be due to, but not limited to, the accumulation of carbonaceous material on the catalyst over time. A "deactivated" or "poisoned" catalyst is substantially free of activity to catalyze aromatization reactions or catalyze decomposition reactions. The spent catalyst can be contacted with a catalyst poisoning agent that effectively quenches the activity of the resulting deactivated or poisoned catalyst. In some aspects, the "fresh" catalyst has activity X, the "spent" catalyst has activity Y, and the "deactivated" or "poisoned" catalyst has activity Z. , So that Z<Y<X. Thus, the activity of the spent catalyst is less than that of the fresh catalyst, but greater than that of the deactivated/poisoned catalyst (which has no measurable catalytic activity). Comparison of catalyst activity (and other reforming performance characteristics such as aromatics yield and selectivity) means using the same catalyst production equipment (batch), on the same equipment and with the same test method and Tested under conditions.

The amounts of any components or materials present on the catalysts described herein are by weight, such as wt% or ppmw (ppm by weight), unless otherwise noted. These components or materials can include, for example, the amount of carbon, the amount of fluorine, the amount of chlorine, the amount of platinum, and the like.

In general, groups of elements are designated using the numbering scheme shown in the edition of the Periodic Table of the Elements, published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, the group of elements is a common name assigned to the group, such as alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Group 3-12 elements, 8 It may be indicated with a noble metal for the 10 group elements and a halogen or halide for the 17 group elements.

For any particular compound or group disclosed herein, any (general or specific) name or structure presented is meant to refer to all possible groups of substituents, unless otherwise stated. It is intended to include conformers, regioisomers, stereoisomers, and mixtures thereof. Names or structures refer to all enantiomers, diastereomers, and other optical isomers (if any) of either enantiomers or racemic forms, as well as stereoisomers, as would be recognized by those of skill in the art, unless otherwise indicated. It also includes a mixture of isomers. For example, general references to hexane include n-hexane, 2-methyl-pentane, 3-methyl-pentane, 2,2-dimethyl-butane, and 2,3-dimethyl-butane, with general references to butyl groups. Specific references include n-butyl, sec-butyl, isobutyl, and t-butyl groups.

In one aspect, a chemical “group” is defined according to how it is formally derived from a reference or “parent” compound, for example, even if the group is not effectively synthesized in such a manner. It can be defined or described by the number of hydrogen atoms removed from the parent compound to generate the group. These groups may be utilized as substituents, or coordinated or bonded to the metal atom. By way of example, an "alkyl group" may be formally derived by removing a hydrogen atom from an alkane. The present disclosure that substituents, ligands, or other chemical moieties can make up a particular "group" means that when the group is used as described, the well-known rules of chemical structure and bonding. Means to obey. When a group is described as being “derived by,” “derived from,” “formed by,” or “formed by,” such terms are used in the formal sense and are otherwise provided. Unless specified to the contrary, or context requires otherwise, it is not intended to reflect any particular synthetic method or procedure.

Various numerical ranges are disclosed herein. When any type of range is disclosed or claimed, it includes the endpoints of the range and subranges and combinations of subranges subsumed therein unless otherwise stated. Each possible number obtained is intended to be individually disclosed or claimed. As a representative example, the present application contemplates that the methods provided herein contain F and Cl in an aspect in a molar ratio of F:Cl within the range of about 0.5:1 to about 4:1. It is disclosed that a catalyst can be used. With the disclosure that the F:Cl molar ratio can be in the range of about 0.5:1 to about 4:1, the molar ratio can be any molar ratio within the range, and, for example, about 0.5:1, about 0.6:1, about 0.7:1, about 0.8:1, about 0.9:1, about 1:1, about 2:1, about 3:1, or It is intended to state that it can be equal to about 4:1. Additionally, the F:Cl molar ratio can range from about 0.5:1 to about 4:1 (eg, the molar ratio can range from about 0.5:1 to about 2:1). Can be) and also includes any combination in the range of about 0.5:1 to about 4:1. Similarly, all other ranges disclosed herein are to be construed in the same manner as this example.

The term "about" is an approximation that includes amounts, sizes, formulations, parameters, and other amounts and characteristics that are not, and need not be, exact, but greater or less than desired. It may be a value and is meant to reflect tolerances, conversion factors, rounding, measurement error, and other factors known to those of ordinary skill in the art. In general, an amount, size, formulation, parameter, or other amount or characteristic is "about" or "approximately" whether or not explicitly stated to be. The term "about" also includes different amounts due to different equilibrium conditions of the composition resulting from a particular initial mixture. Whether modified by the term "about" or not, the claims include their equivalents. The term "about" can mean within 10% of the reported numerical value, preferably within 5% of the reported numerical value.

The term "substituted," when used to describe a compound or group, for example, when referring to a substituted analog of a particular compound or group, refers to any formally replacing hydrogen in that group. The non-hydrogen moieties are intended to be illustrative and non-limiting. One or more groups are also referred to herein as "unsubstituted," or "non-substituted," which refers to the original group in which the non-hydrogen moieties do not replace hydrogen atoms within the group. Can also be represented by equivalent terms such as ". Unless otherwise noted, "substituted" is intended to be non-limiting and includes inorganic or organic substituents, as will be appreciated by those of skill in the art.

The term "hydrocarbon" as used herein refers to a compound containing only carbon and hydrogen atoms. Other identifiers, if any, may be utilized to indicate the presence of a particular group in a hydrocarbon (eg, halogenated hydrocarbon replaces an equivalent number of hydrogen atoms in the hydrocarbon 1 Indicates the presence of one or more halogen atoms).

An "aromatic" compound is a compound that includes a cyclic conjugated double bond system according to the Hückel (4n+2) rule and containing (4n+2) π electrons, where n is an integer from 1 to 5. Aromatic compounds correspond to "arenes" (hydrocarbon aromatic compounds such as benzene, toluene, and xylene), and "heteroarenes" (continuous pi-electron system characteristic of aromatic systems and Hückel's rule (4n+2)). From an arene by substitution of one or more methine (-C=) carbon atoms of a cyclic conjugated double bond system with a trivalent or divalent heteroatom in such a way as to maintain the number of out-of-plane pi electrons. Heteroaromatic compounds derived from a natural source). As disclosed herein, the term "substituted" can be used to describe an aromatic group, arene, or heteroarene, where the non-hydrogen moiety is the formal hydrogen atom in the compound. And is intended to be non-limiting unless otherwise stated.

The term "alkane" as used herein means a saturated hydrocarbon compound. Other identifiers, if any, may be utilized to indicate the presence of a particular group in the alkane (eg, a halogenated alkane may replace one or more hydrogen atoms replacing an equivalent number of hydrogen atoms in the alkane). Indicates the presence of a halogen atom). The term "alkyl group" is used herein according to the definition provided by IUPAC and is a monovalent group formed by removing a hydrogen atom from an alkane. Alkanes or alkyl groups can be linear or branched unless otherwise stated.

“Cycloalkane” is a saturated cyclic hydrocarbon, with or without side chains, such as cyclobutane, cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. Other identifiers, if any, may be utilized to indicate the presence of a particular group in a cycloalkane (eg a halogenated cycloalkane replaces an equivalent number of hydrogen atoms in a cycloalkane). Indicates the presence of one or more halogen atoms).

The term "halogen" has its ordinary meaning. Examples of halogen include fluorine, chlorine, bromine, and iodine.

The term “contacting”, unless stated otherwise, describes a method, process, and composition in which components are contacted or combined together in any order, in any manner, for any length of time. As used herein. For example, the components can be contacted by blending or mixing. Further, unless otherwise stated, contacting any of the components can occur in the presence or absence of any other component of the methods, processes, and compositions described herein. Combining additional materials or components can be done by any suitable technique. Further, "contacting" two or more components can result in a solution, slurry, mixture, reaction mixture, reaction product.

Molar selectivity is defined as:

Conversion is defined as the number of moles converted per mole of "convertible" hydrocarbon fed.

In these equations,
Indicates the molar flow rate in a continuous reactor or the number of moles in a batch reactor.

As used herein, the term "convertible hydrocarbon", "convertible C ₆ type", or "convertible C ₇ species" readily reacts with aromatization process conditions Refers to hydrocarbon compounds that form aromatic hydrocarbons. A "non-convertible hydrocarbon" is a highly branched hydrocarbon that does not readily react to form aromatic hydrocarbons under the aromatization process conditions. "Unconvertible hydrocarbon" means a highly branched hydrocarbon having 6 or 7 carbon atoms with 1 internal quaternary carbon, or 6 carbon atoms and 2 adjacent internal tertiary carbons. May be included, or mixtures thereof. "Convertible C ₆ species" is one internal quaternary carbon or two adjacent hydrocarbon containing 6 carbons containing no internal tertiary carbon, for example, n- hexane, 2-methyl - pentane , 3-methyl-pentane, cyclohexane, and methylcyclopentane. "Convertible _{C 7} species" is a hydrocarbon containing 7 carbons containing no internal quaternary carbon, e.g., n- heptane, 2-methyl - hexane, 3-methyl - hexane, 2,3-dimethyl - Pentane, 2,4-dimethyl-pentane, methylcyclohexane, and dimethylcyclopentane. Highly branched hydrocarbons having 6 or 7 carbon atoms and one internal quaternary carbon are, for example, 2,2-dimethylbutane, 2,2-dimethylpentane, 3,3-dimethylpentane, and It may include 2,2,3-trimethylbutane. Highly branched hydrocarbons with 6 carbon atoms and 1 adjacent internal tertiary carbon can include, for example, 2,3-dimethylbutane. Non-convertible, highly branched hydrocarbons do not readily convert to aromatic products and instead tend to convert to lighter hydrocarbons under aromatization process conditions.

Although any methods and materials similar or equivalent to those disclosed herein can be used in the practice or testing of the present invention, typical methods and materials are described herein.

All publications and patents mentioned in this specification are herein incorporated by reference for the purpose of explanation and disclosure, for example, the compositions and methodologies described in the publication are associated with the invention. May be used.

The following detailed description refers to the accompanying drawings. Wherever possible, the same or similar reference numbers are used in the drawings and the following description to refer to the same or similar elements or features. While various aspects of the invention have been described, modifications, adaptations, and other implementations are possible. For example, substitutions, additions, or modifications can be made to the elements illustrated in the figures, and the methods described herein replace, rearrange, or add steps to the disclosed methods. Can be modified by Therefore, the following detailed description and its illustrative aspects do not limit the scope of the invention.

Beneficially, the aromatization reactor vessels, reactor systems, and reforming processes disclosed herein utilize poisoned or deactivated aromatization catalysts in place of spent aromatization catalysts. Unexpectedly resulting in improved aromatic yield and selectivity. Surprisingly, by selectively poisoning the "spent" catalyst in the outer reforming zone (closest to the outer annulus), the overall aromatic yield and selectivity in the reactor is surprising. Can be increased.

Aromatization Reactor Vessels and Systems Generally, aromatization reactor vessels consistent with the present invention include (i) a reactor wall, (ii) a catalyst bed positioned within the reactor vessel, and (iii) a reaction. An outer annulus positioned between the vessel wall and the outer particle barrier, the outer particle barrier and the outer annulus surrounding the catalyst bed; and (iv) a reactor inlet for feed stream. , (V) a reactor outlet connected to the central tube, the central tube being positioned within the reactor vessel and surrounded by the catalyst bed. The catalyst bed can include an outer reforming zone and an inner reforming zone, the outer reforming zone including a deactivated first aroma including a first transition metal and a first catalyst support. The aromatization catalyst is included and the inner reforming zone includes a second aromatization catalyst including a second transition metal and a second catalyst support. A flow path for the feed stream begins at the reactor inlet, continues to the outer annulus, through the outer particle barrier, the outer reforming zone, and the inner reforming zone, to the central tube, and to the reactor outlet. ..

FIG. 1 illustrates an aromatization reactor vessel 110 consistent with the present invention. Although not limited thereto, the aromatization reactor vessel 110 is described herein for use in the catalytic conversion of non-aromatic hydrocarbons to produce aromatic hydrocarbons, examples of which are shown. Include benzene, toluene, or xylene, as well as mixtures thereof. The aromatization reactor vessel 110 of FIG. 1 includes a reactor wall 120, a central tube 135 surrounded by a catalyst bed 130, an outer particle barrier 137 surrounding the catalyst bed, and an outer particle barrier 137 between the reactor wall 120. An outer annular portion 125 of Reactor vessel 110 may further include a reactor inlet 150 for the feed stream, a top cover plate 138, and a reactor outlet 160 through which the reactor effluent stream flows. Reactor outlet 160 is connected to central tube 135 as shown in FIG. The catalyst bed 130 includes an outer reforming zone 170 and an inner reforming zone 180. The arrows in FIG. 1, for example, begin at the reactor inlet 150, then by the upper cover plate 138 to the outer annulus 125, then the outer particle barrier 137, and the catalyst bed 130 (first outer reforming zone 170, then inner reforming). Illustrating a typical flow path for the feed stream entering the aromatization reactor vessel 110 through the zone 180), through the central tube 135 and finally as the reactor effluent to the reactor outlet 160. To do.

In FIG. 1, the outer particle barrier 137 in the aromatization reactor vessel 110 can be formed in any number of ways, including using scallops, outer baskets, and the like. The outer basket more closely resembles that shown in FIG. The outer basket can have a circular cross-sectional shape. The outer basket has openings that allow passage of the feed stream but not catalyst particles. Passage of the feed stream can be accomplished by forming a slot in the outer basket, forming a portion of the outer basket with a screen or mesh, or a combination thereof. The outer basket can be made from sub-sections assembled inside the reactor vessel.

If desired, the outer annulus 125 can include any suitable flow-influencing element within the flow path to facilitate flow through the catalyst bed. For example, a "scallop" is a conduit that is installed adjacent to and vertically along the inner wall of a reactor vessel. The scallops can have a semi-circular cross section or a trapezoidal cross-sectional shape. The scallops have openings that allow the passage of the feed stream but not the catalyst particles. Passage of the feed stream can be accomplished by forming a slot in the scallop and forming a portion of the outer scallop with a screen or mesh, or a combination thereof. The scallops are pressed against the inside of the reactor wall 120 such that the scallop slots, screens or meshes face the catalyst bed 130. Scallops are typically, but not limited to, 8 to 14 inches wide. In one aspect, the screen can include welding wires and rods. In a further aspect, the screen can include welded Johnson Screens® Vee-Wire® and rods. As a further improvement, the slots and screens on the scallops can be oriented vertically to allow catalyst particles to move up and down during processing without being abraded by the ends of the screens or slots. During operation of the aromatization reactor vessel, the scallops can distribute the feed stream along the inner wall and collect the feed stream from the catalyst bed, depending on the direction of flow. In standard flow, the feed flows radially across catalyst bed 130 to the center of the reactor vessel. At the center of the reactor vessel is the process outlet conduit, which may be a vertical perforated tube, also referred to as central tube 135.

The reactor wall 120, central tube 135, and other elements of the aromatization reactor vessel 110 in FIG. 1 may be generally cylindrical in shape, although other geometries and orientations may be used. .. For example, as an alternative to a circular cross section (when viewed from the top, such as from the reactor inlet 150), the central tube can have a rectangular, oval, or oval cross section. Nevertheless, in certain aspects of the invention, the center tube 135 and the reactor wall 120 are concentrically arranged, and the center tube 135 and the catalyst bed 130 are concentrically arranged, such that the center tube 135 and the catalyst bed are 130 and the reactor wall 120 are arranged concentrically and the central tube 135, the catalyst bed 130 and the outer particle barrier 137 are arranged concentrically or the central tube 135, the catalyst bed 130, the outer particle barrier 137, And the reactor walls 120 are arranged concentrically.

The reactor wall 120, center tube 135, top cover plate 138, outer particle barrier 137, and other surfaces within the aromatization reactor vessel 110 can be constructed of any suitable metallic material, the choice of which is , The desired operating temperature, the desired operating pressure, inertness to the reactor contents (eg, catalyst, H ₂ , aromatic hydrocarbons, non-aromatic hydrocarbons), among other factors. Typical metallic materials include austenitic stainless steels, including 304, 316, 321, 347, 410S, 600, or 800 stainless steels. Additionally, any suitable material, compound, alloy, or coating or layer containing a metal such as tin may be used on any reactor surface (eg, reactor wall 120 or central tube 135) for carburization and Typical protective layer materials that can provide resistance to metal dust are U.S. Pat. Nos. 5,866,743, 6,548,030, 8,119,203, and No. 9,085,736, which is incorporated herein by reference in its entirety. As shown by the dashed line in FIG. 1, the central tube 135 may be porous to allow flow therethrough, but is so porous that catalyst particles from the catalyst bed 130 can enter the central tube 135. Not sex. Accordingly, the central tube 135 can include screens, mesh sections, perforated metal sheets, or combinations thereof within the reactor vessel 110. In one aspect, the central tube 135 can include welding wires and rods. In a further aspect, the screen can include welded Johnson Screens® Vee-Wire® and rods. As a further improvement, the slots and screens on the central tube 135 can be vertically oriented to allow catalyst particles to move up and down during processing without being abraded by the ends of the screens or slots. ..

The aromatization reactor vessel 110 may be configured for operating temperatures that are typically in the range of 350°C to 600°C. In one aspect, the reactor vessel 110 can be configured to reduce the temperature from the outer annulus 125 to the central tube 135, while in another aspect, the reactor vessel 110 can be configured from the outer reforming zone 170 to the inside. It can be configured to reduce the temperature to the reforming zone 180. In these and other aspects, the reactor vessel 110 can be configured for, but not limited to, radial flow. For example, a conventional packed bed reactor can be used in aspects of the invention.

Similarly, the reactor vessel 110 is often at least 20 psig (139 kPag), at least 25 psig (172 kPag), or at least 30 psig (207 kPag), and in some aspects up to about 60 psig (414 kPag) to about 100 psig (689 kPag). Can be configured for any suitable operating pressure, which is Thus, typical operating pressures include about 20 psig (139 kPag) to about 100 psig (689 kPag), or about 25 psig (172 kPag) to about 60 psig (414 kPag).

Although not shown in FIG. 1, reactor vessel 110 contains braces, clamps, straps, etc., and combinations thereof to secure central tube 135, outer particle barrier 137, and other interior reactors. Can be done and will be readily recognized by one of ordinary skill in the art.

Additionally, the reactor vessel 110 may further comprise an integrated heat exchange system around at least a portion of the reactor vessel to control (heat or cool) the temperature within the reactor vessel, if desired. it can. Additional information regarding the features and designs of aromatization reactor vessels that may be used within the aromatization reactor vessels described herein may be found in US Pat. Nos. 6,548,030 and 7,544. No. 335, No. 7,582,272, No. 8,119,203, and No. 9,085,736, which are incorporated herein by reference in their entirety.

Also shown in the aromatization reactor vessel 110 of FIG. 1 is a catalyst bed 130 containing an outer reforming zone 170 and an inner reforming zone 180. The outer reforming zone is also referred to herein as the first reforming zone and the inner reforming zone is also referred to herein as the second reforming zone. Consistent with aspects disclosed herein, the outer (or first) reforming zone comprises a deactivated first aromatization catalyst comprising a first transition metal and a first catalyst support. And the inner (or second) reforming zone can include a second aromatization catalyst that includes a second transition metal and a second catalyst support.

The deactivated (or poisoned) first aromatization catalyst in the outer reforming zone can be configured to generally not catalyze the aromatization reaction. For example, the aromatic yield of the deactivated first aromatization catalyst may be less than 10 wt%, or less than 5 wt%, or virtually zero, such as under the test methods disclosed in the Examples below. (No catalytic activity). Additionally or alternatively, the deactivated (or poisoned) first aromatization catalyst in the outer reforming zone can generally be configured to not catalyze the cracking reaction.

The deactivated first aromatization catalyst may result from a spent aromatization catalyst in contact with a catalyst poisoning agent, the catalyst poisoning agent being a material configured to bind to a transition metal. , So that the transition metal does not catalyze the aromatization reaction and/or the decomposition reaction. The mechanism by which the catalyst poison results in a deactivated aromatization catalyst that does not catalyze the aromatization and/or decomposition reaction is not so limited. For example, the catalyst poisoning agent may be less than 10 wt%, less than 5 wt%, in platinum sintering, platinum agglomeration, and/or pore plugging, and aromatic yield of the deactivated catalyst, or Materials may be included that cause any other suitable mechanism that causes virtually zero (no catalytic activity), additionally or alternatively resulting in a deactivated catalyst that does not catalyze the decomposition reaction.

In one aspect, the amount of carbon on the deactivated first aromatization catalyst is from about 1 to about 10 wt%, about 1 to about 5 wt%, about 1.5 to about 7 wt%, or It can be in the range of about 1.5 to about 3% by weight. Additionally, the amount of carbon on the second aromatization catalyst can often be less, such as less than about 0.9% by weight, or less than about 0.5% by weight, with a typical range being , About 0.01 wt% to about 0.9 wt%, about 0.01 wt% to about 0.5 wt%, or about 0.02 wt% to about 0.5 wt%.

Although not limited thereto, the weight ratio (or volume ratio) of the amount of catalyst in the outer reforming zone to the amount of catalyst in the inner reforming zone is from about 10:1 to about 1:10, about. It can be within the range of 5:1 to about 1:5, or about 1:3 to about 3:1 (outer:inner). In some aspects, the outer reforming zone contains less catalyst than the inner reforming zone, and in these aspects, the outer:inner ratio is from about 1:1.2 to about 1:10, about 1. :1.5 to about 1:5, or about 1:2 to about 1:6, and the ratios can be on a weight basis or a volume basis. As will be appreciated by those skilled in the art, the relative size of the outer reforming zone and the inner reforming zone (or the relative amount of catalyst therein) is such that more catalyst within the catalyst bed is deactivated or poisoned. Can change.

An unexpected advantage of the reactor vessels disclosed herein may be improved aromatic yield, improved aromatic selectivity, or both. In one aspect, the reactor vessel is more than that obtained using the used first aromatization catalyst in the outer reforming zone instead of the deactivated first aromatization catalyst. It can be configured for a large, aromatic yield at the reactor outlet. Because of this, it is surprising that the spent catalyst (catalyst with poor or unacceptable yield performance) in the outer reforming zone of the catalyst bed has been deactivated or poisoned (aromatic yield). Catalyst) can result in greater overall aromatic yield. In another embodiment, the reactor vessel is more than that obtained using the used first aromatization catalyst in the outer reforming zone instead of the deactivated first aromatization catalyst. Can be configured for greater aromatic selectivity at the reactor outlet. For this reason and also surprisingly, spent catalysts (catalysts with generally poor or unacceptable selectivity performance) in the outer reforming zone of the catalyst bed have been deactivated or poisoned (aromatic selective). The substitution of non-active catalysts) can lead to greater overall aromatic selectivity.

The first catalyst carrier and the second catalyst carrier can independently comprise zeolite, amorphous inorganic oxide, or any mixture or combination thereof. For example, large pore zeolites can often have average pore sizes in the range of about 7Å to about 12Å, non-limiting examples of large pore zeolites include L-zeolite, Y-zeolite, mordenite, omega. Zeolite, beta zeolite and the like can be mentioned. Medium pore zeolites can often have average pore sizes in the range of about 5Å to about 7Å. Amorphous inorganic oxides can include, but are not limited to, aluminum oxide, silicon oxide, titania, and combinations thereof. The first catalyst carrier and the second catalyst carrier may be the same or different.

The term "zeolites" generally refers to a particular group of hydrated crystalline aluminosilicates. These zeolites exhibit a network of SiO ₄ and AlO ₄ tetrahedra in which aluminum atoms and silicon atoms are crosslinked in a three-dimensional framework by sharing oxygen atoms. Within this framework, the ratio of oxygen atoms to the sum of aluminum and silicon atoms may be equal to 2. The skeleton typically exhibits a negative ionic valency that can be equilibrated by including intracrystalline cations such as metals, alkali metals, alkaline earth metals, hydrogen, or combinations thereof.

In some aspects, the first catalyst support and/or the second catalyst support can include L-type zeolite. L-type zeolitic supports are a sub-group of zeolitic supports that can contain a molar ratio of oxides according to the formula: M _{2 /n} OAl ₂ O ₃ xSiO ₂ yH ₂ O. In this formula, "M" is barium, calcium, cerium, lithium, magnesium, potassium, sodium, strontium, zinc, or a combination thereof, as well as the other without substantially changing the basic crystal structure of the L-type zeolite. The replaceable cation(s) are designated, such as non-metallic cations such as hydronium and ammonium ions, which can be replaced by the replaceable cations of. In the formula, "n" represents the valence of "M";"x" is 2 or more; "y" is the number of water molecules contained in the zeolite channels or interconnected voids.

In one aspect, the first catalyst support and/or the second catalyst support can comprise potassium L-type zeolite, also referred to as K/L-type zeolite, while in another aspect, the first catalyst The support and/or the second catalyst support can include barium ion exchanged L-type zeolite. As used herein, the term "K/L-type zeolite" refers to an L-type zeolite in which the major cation M incorporated in the zeolite is potassium. K/L type zeolites may be cation exchanged (eg with barium) or impregnated with a transition metal and one or more halides to produce a transition metal impregnated halogenated zeolite or a KL supported transition metal halide zeolite catalyst. be able to.

In the first and second catalyst supports, the zeolite may be bound to a support matrix (or binder), non-limiting examples of which are silica, alumina, magnesia, boria, titania, zirconia. , Various clays, and the like, including mixed oxides thereof, and mixtures thereof. For example, the first catalyst support and/or the second catalyst support can include a binder that includes alumina, silica, mixed oxides thereof, or mixtures thereof. The zeolite can be combined with the binder using any method known in the art. In a particular embodiment of the present invention, the first catalyst support, the second catalyst support, or both the first catalyst support and the second catalyst support, may comprise silica-bound K/L-type zeolite.

Without limitation, the first catalyst support and the second catalyst support can independently comprise from about 5% to about 35% by weight binder. For example, the first catalyst support and the second catalyst support can independently comprise from about 5% to about 30% by weight, or from about 10% to about 30% by weight binder. These weight percentages are based on the total weight of the (first or second) catalyst support.

The deactivated first aromatization catalyst can include a first transition metal and a first catalyst support, and the second aromatization catalyst can include a second transition metal and a second catalyst. A carrier can be included. The first transition metal and the second transition metal can be the same or different and can include Group 7-11 transition metals, or, alternatively, Group 8-11 transition metals. In some aspects, the deactivated first aromatization catalyst and/or second aromatization catalyst can include a Group 14 metal, such as tin, while in other aspects, The first transition metal and/or the second transition metal can include transition metals, non-limiting examples of suitable transition metals include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, It can include rhenium, platinum, gold, silver, copper, etc., or a combination of two or more transition metals.

For example, the deactivated first aromatization catalyst and/or the second aromatization catalyst can include platinum, rhenium, tin, iron, gold, or any combination thereof. Alternatively, the first transition metal and/or the second transition metal can include a transition metal of Groups 7-11 (eg, one or more of platinum, rhenium, and gold), and In one aspect, the first transition metal and/or the second transition metal can include a Group 10 transition metal, and in yet another aspect, the first transition metal and the second transition metal are platinum. (Pt) may be included.

Typically, the deactivated first aromatization catalyst and second aromatization catalyst can include from about 0.1 wt% to about 10 wt% transition metal. In another aspect, the deactivated first aromatization catalyst and/or second aromatization catalyst can include from about 0.3 wt% to about 5 wt% transition metal. In yet another aspect, the deactivated first aromatization catalyst and/or second aromatization catalyst comprises from about 0.3% to about 3% by weight transition metal, or about 0.5%. % To about 2% by weight transition metal may be included. These weight percentages are based on the total weight of the (first or second) aromatization catalyst. In the situation where the transition metal comprises platinum, the deactivated first aromatization catalyst and/or second aromatization catalyst may comprise from about 0.1 wt% to about 10 wt% platinum, alternatively , About 0.3 wt.% to about 5 wt.% platinum, alternatively about 0.3 wt.% to about 3 wt.% platinum, or alternatively about 0.5 wt.% to about 2 wt.%. It can include platinum.

In one aspect, the deactivated first aromatization catalyst, second aromatization catalyst, or both can include platinum on the L-type zeolite. In another aspect, the deactivated first aromatization catalyst, second aromatization catalyst, or both can include platinum on K/L-type zeolite. In yet another aspect, the deactivated first aromatization catalyst, the second aromatization catalyst, or both, can include platinum on K/L zeolite bound to silica.

Additionally, the deactivated first aromatization catalyst and second aromatization catalyst may further comprise a halogen such as chlorine, fluorine, bromine, iodine, or a combination of two or more halogens. it can. For example, the deactivated first aromatization catalyst and/or the second aromatization catalyst can include chlorine, fluorine, or both chlorine and fluorine.

Chlorine is present in the deactivated first aromatization catalyst, the second aromatization catalyst, or both, in an amount of about 0.01 wt% to about 5 wt%, about 0.1 wt% to about 0.1 wt%. It can be present in an amount of 2% by weight, or about 0.3% by weight to about 1.3% by weight. Similarly, the deactivated first aromatization catalyst, the second aromatization catalyst, or both, comprises from about 0.01% to about 5% by weight fluorine, from about 0.1% by weight to about 0.1% by weight. It can include about 2 wt% fluorine, or about 0.3 wt% to about 1.3 wt% fluorine. These weight percentages are based on the total weight of each aromatization catalyst. In some embodiments, the deactivated first aromatization catalyst, the second aromatization catalyst, or both include chlorine and fluorine, and typically the fluorine:chlorine molar ratio is independent. And can range from about 0.2:1 to about 4:1. Other suitable molar ratios of F:Cl include the following non-limiting ranges: about 0.3:1 to about 4:1, about 0.5:1 to about 4:1, about 0.2:1 to. It can include about 2:1, about 0.3:1 to about 2:1, or about 0.5:1 to about 2.5:1.

Representative and non-limiting examples of catalysts that may be used as the first aromatization catalyst (before deactivation or poisoning) and/or the second aromatization catalyst are US Pat. No. 5,196. No. 631, No. 6,190,539, No. 6,406,614, No. 6,518,470, No. 6,812,180, No. 7,153,801, and No. 7,932,425, the disclosures of which are hereby incorporated by reference in their entireties.

Aromatization reactor vessel systems are also included herein, and such systems may generally include two or more aromatization reactor vessels in series, at least one of which is an aromatic Any of the reforming reactor vessels (ie, having a catalyst bed 130 containing an outer reforming zone 170 and an inner reforming zone 180). For example, an exemplary reactor system may include any of two to eight vessels in series, two to seven vessels, three to eight vessels, four to seven vessels, five vessels, six vessels, seven vessels, or eight vessels in series. A suitable number of reactor vessels can be included. The reactor system is configured for a single passage of non-aromatic hydrocarbons through a series of reactor vessels, or the reactor system is configured to remove unreacted non-aromatic hydrocarbons from a series of first The unreacted non-aromatic hydrocarbons may be subsequently recycled to the reactor vessel so as to be separated from the aromatic hydrocarbons.

In the series of reactor vessels, the particular vessel (or vessels) comprising the catalyst bed 130 containing the outer reforming zone 170 and the inner reforming zone 180 is not particularly limited. For example, a reactor vessel with a catalyst bed 130 containing an outer reforming zone 170 and an inner reforming zone 180 may include a series of first, second, third, fourth, or fifth vessels, or series of. It can be a third or fourth container. Additionally, there may be more than one reactor vessel with a catalyst bed containing an outer reforming zone and an inner reforming zone.

The aromatization reactor vessel system can further include a furnace in front of any series of reactor vessels or each reactor vessel, the furnace comprising up to about 350° C. to about 600° C. reactor vessel operating temperature. It may be possible to heat any feed stream. Typically, the reactor vessel system contains a furnace before the series of first reactor vessels. Also, typically, the reactor vessel system contains a furnace in front of each reactor vessel in the series. Each furnace may be configured to heat the reactor effluent in front of the series of reactor vessels to a temperature of about 350° C. to about 600° C. before entering the next vessel in the series. A transfer tube may be positioned between each furnace and each upstream and downstream reactor vessel, and may connect each furnace to each upstream and downstream reactor vessel.

FIG. 2 presents an exemplary embodiment of an aromatization reactor vessel system 200 that includes an aromatization reactor vessel with a catalyst bed 130 containing an outer reforming zone 170 and an inner reforming zone 180. .. In FIG. 2, six reactor vessels 271, 272, 273, 274, 275, 276 are shown in series with corresponding furnaces 281, 282, 283, 284, 285, 286 for each respective one in system 200. It precedes the reactor vessel. The furnaces 281, 282, 283, 284, 285, 286 of FIG. 2 can heat or reheat any feed stream or reactor effluent to a reactor vessel operating temperature of about 350° C. to about 600° C. Can be The feed stream 252 enters the first furnace 281 and then the first reactor vessel 271. Each reactor vessel contacts the feed stream with an aromatization catalyst to catalytically convert at least a portion of the non-aromatic hydrocarbons, such as aromatic hydrocarbons (eg, benzene, toluene, xylenes, etc.). That combination). Gradually more non-aromatic hydrocarbons are converted to aromatic hydrocarbons, starting with the more easily converted non-aromatic hydrocarbons as they traverse each reactor vessel in series. Final reactor effluent 262 exits the last reactor vessel 276 in system 200.

The aromatization reactor vessel with the catalyst bed 130 containing the outer reforming zone 170 and the inner reforming zone 180 can be installed at any suitable location within the system 200 and series of reactor vessels, Two or more such reactor vessels can be used. The aromatization reactor vessel system 200 shown in FIG. 2 contains 6 reactor vessels in series, for example 2-8 reactor vessels, 2-7 reactor vessels, 3-8 reactions. Use any suitable number of reactor vessels in series, such as reactor vessels, 4-7 reactor vessels, 5 reactor vessels, 6 reactor vessels, 7 reactor vessels, or 8 reactor vessels can do. The reactor system may be configured for a single passage of non-aromatic hydrocarbons through a series of reactor vessels, or the reactor system may include unreacted non-aromatic hydrocarbons in series with the first non-aromatic hydrocarbons. The unreacted non-aromatic hydrocarbons may be subsequently recycled to the reactor vessel so as to be separated from the aromatic hydrocarbons.

Modification Method Aspects of the present invention also relate to an aromatization or modification method. A first reforming method provided herein is to provide (a) a radial flow reactor comprising a catalyst bed, wherein the catalyst bed comprises an outer (or first) reforming zone and an inner reforming zone. A (or a second) reforming zone, the outer reforming zone comprises a spent first aromatization catalyst comprising a first transition metal and a first catalyst support, and the inner reforming zone comprises Providing a second aromatization catalyst, comprising a second transition metal and a second catalyst support, and (b) a catalyst poisoning agent (or catalyst deactivator) for the radial flow reactor. And at least a portion of the spent first aromatization catalyst in the outer reforming zone (to partially or completely deactivate the portion of the used first aromatization catalyst). And (c) introducing a hydrocarbon feed into the radial flow reactor containing the catalyst bed and contacting the hydrocarbon feed with the catalyst bed under reforming conditions to produce an aromatic product. Can include (or consist essentially of, or consist of).

The second reforming method provided herein introduces a first hydrocarbon feed into a radial flow reactor containing a catalyst bed (A) and under a first reforming condition, a first hydrocarbon feed. Contacting the hydrocarbon feed with a catalyst bed to produce a first aromatic product, the catalyst bed comprising an outer (or first) reforming zone and an inner (or second) reforming zone. A reforming zone may be included, an outer reforming zone may include a first aromatization catalyst that includes a first transition metal and a first catalyst support, and an inner reforming zone may include a second reforming zone. A second aromatization catalyst, comprising: a transition metal and a second catalyst support, forming and forming (B) a used first aromatization catalyst in the outer reforming zone. Performing step (A) for a sufficient period of time, and (C) introducing a catalyst poisoning agent (or catalyst deactivator) into the radial flow reactor and Contacting with at least a portion of the spent first aromatization catalyst (to partially or fully deactivate the portion of the used first aromatization catalyst); and (D) a catalyst. Introducing a second hydrocarbon feed into a radial flow reactor containing the bed and contacting the second hydrocarbon feed with the catalyst bed under second reforming conditions to produce a second aromatics product. Producing (or consisting essentially of, or consisting of) an article. Step (B) in this second reforming method shows that step (A) can be carried out for a period of time sufficient for the first aromatization catalyst to be "spent". As discussed herein above, "spent" catalyst typically means catalytic activity, hydrocarbon feed conversion, yield to desired product(s), desired product(s). The catalyst has unacceptable performance at one or more of its operating parameters such as selectivity to (or) or maximum operating temperature or pressure drop across the reactor, but is not limited thereto. Once the first aromatization catalyst is “spent”, among other things, the catalyst deactivation/poisoning step (C) may be carried out.

Generally, features of the first and second processes (eg, first and second hydrocarbon feeds, first and second aromatization catalysts, first and second aromatic products, among others). , Inner and outer reforming zones) are independently described herein, and these features may be combined in any combination to further describe the disclosed reforming methods. Moreover, unless otherwise stated, other process steps may be performed before, during, and/or after any of the steps listed in this first and second method.

In these methods, the hydrocarbon feed, the first hydrocarbon feed, and a second hydrocarbon feed are independently, C ₆ -C ₉ alkanes and / or cycloalkanes or C ₆ -C _8, It may contain non-aromatic hydrocarbons such as alkanes and/or cycloalkanes. Further, the hydrocarbon feed, the first hydrocarbon feed, and the second hydrocarbon feed can independently include hexane, heptane, or a combination thereof. The first hydrocarbon feed and the second hydrocarbon feed may be the same or different. Typically, the aromatic product, the first aromatic product, and the second aromatic product independently formed by these reforming processes comprise benzene, toluene, or a combination thereof. You can Suitable reforming conditions, first reforming conditions, and second reforming conditions may independently include the same ranges disclosed above with respect to reactor vessel operating conditions. For example, the reforming conditions, the first reforming conditions, and the second reforming conditions are independently reforming temperatures in the range of about 350°C to about 600°C (or about 400°C to about 600°C). , And a reforming pressure in the range of about 20 psig (138 kPag) to about 100 psig (689 kPag) (or about 25 to about 60 psig (about 172 to about 414 kPag)). Further, the temperature of the hydrocarbon feed, the first hydrocarbon feed, and the second hydrocarbon feed can drop from the outer reforming zone to the inner reforming zone. Other suitable non-aromatic hydrocarbon feed materials, aromatic hydrocarbon products, and aromatics for use in the disclosed process for catalytically converting non-aromatic hydrocarbons to aromatic hydrocarbons Modification or modification conditions are known to those skilled in the art, and for example, US Pat. Nos. 4,456,527, 5,389,235, 5,401,386, and 5,401, 365, 6,207,042, 7,932,425, and 9,085,736, the disclosures of which are incorporated herein by reference in their entireties. Be done.

In these methods, the first catalyst support and the second catalyst support may be the same or different and are independently present as suitable catalyst support materials for use in the aromatization reactor vessel. It can be any of the catalyst supports disclosed in the text. For example, the first catalyst support and/or the second catalyst support can include silica bound K/L type zeolite. Similarly, the first transition metal and the second transition metal are independently any of the transition metals disclosed herein as being suitable transition metals for use in the aromatization reactor vessel. It could be For example, the first transition metal and the second transition metal can include platinum. Thus, the first aromatization catalyst, the second aromatization catalyst, and the used first aromatization catalyst are independently, for example, based on the total weight of each aromatization catalyst. From about 0.1% to about 10%, from about 0.3% to about 5%, or from about 0.5% to about 2% by weight, within any of the ranges disclosed herein. , Any suitable weight percentage of transition metal (or platinum) or an amount of transition metal (or platinum).

In one aspect, the first aromatization catalyst, the second aromatization catalyst, and the used first aromatization catalyst can comprise platinum on L-type zeolite, while another aspect. Wherein the first aromatization catalyst, the second aromatization catalyst, and the used first aromatization catalyst can include platinum on K/L-type zeolite, and in yet another aspect, , The first aromatization catalyst, the second aromatization catalyst, and the used first aromatization catalyst can include platinum on silica-bound K/L-type zeolite.

The first aromatization catalyst, the second aromatization catalyst, and the used first aromatization catalyst can further include halogen such as chlorine and/or fluorine. Suitable amounts are disclosed herein and often range from about 0.01 wt.% to about 5 wt.%, or about 0.3 to about 1.3 wt.% fluorine and chlorine individually. .. The relative amounts of fluorine and chlorine on each catalyst are also disclosed herein and are generally within the fluorine:chlorine (F:Cl) molar ratio range of about 0.2:1 to about 4:1. Fits in.

In one aspect, the amount of carbon on the spent first aromatization catalyst is from about 1 to about 10% by weight, about 1 to about 5% by weight, about 1.5 to about 7% by weight, or about 1%. It can range from 0.5 to about 3% by weight. Additionally, the amount of carbon on the first and second aromatization catalysts can often be less, such as less than about 0.9% by weight, or less than about 0.5% by weight. Representative ranges for the amount of carbon on the aromatization catalyst and the second aromatization catalyst are independently about 0.01 wt% to about 0.9 wt%, about 0.01 wt% to about 0.01 wt%. It can comprise about 0.5% by weight, or about 0.02% to about 0.5% by weight.

Generally, the activity (eg, aromatic yield) of the second aromatization catalyst is greater than the activity of the used first aromatization catalyst, and additionally or alternatively, the second aromatization catalyst. The aromatic selectivity of the catalyst is greater than the selectivity of the used first aromatization catalyst. Such comparisons are intended to be performed under the same test conditions.

In step (b) of the first reforming method (and step (C) of the second reforming method), the catalyst poisoning agent (or catalyst deactivator) is introduced into the radial flow reactor and the It can be contacted with at least a portion of the spent first aromatization catalyst in the reforming zone, thereby allowing any suitable portion of the spent first aromatization catalyst in the outer reforming zone. Alternatively, the proportion is partially or completely inactivated. The catalyst poison can be added to the reactor in any conventional manner, such as through the reactor inlet or another feed port, if desired. In one aspect, the catalyst poison can be fed to the reactor along with the hydrocarbon feed. Additionally or alternatively, the hydrocarbon feed (eg, the first hydrocarbon feed) can be temporarily stopped or interrupted, then the catalyst poison is fed to the reactor, and then The hydrocarbon feed (eg, the second hydrocarbon feed) to the reactor can be restarted.

The catalyst poisoning (or deactivating) agent can be added to the reactor in any suitable amount. However, in general, the catalyst poison is from about 0.01:1 to about 1:1, about 0.01:1 to about 0.5:1, about 0.05:1 to about 1:1, about 0. 0.05:1 to about 0.5:1, about 0.1:1 to about 0.75:1, about 0.2:1 to about 1:1, about 0.2:1 to about 0.8: Molar ratio within the range of 1, about 0.3:1 to about 0.8:1, about 0.4:1 to about 1:1 or about 0.5:1 to about 0.9:1 (catalyst The poisoning agent can be introduced into the reactor in moles relative to the moles of transition metal in the used first aromatization catalyst. Thus, any amount of the used first aromatization catalyst in the outer reforming zone, from very small amount to virtually all, can be contacted with the catalyst poison. After contacting the used first aromatization catalyst with the catalyst poisoning agent, the aromatic yield of the used (poisoned or deactivated) used first aromatization catalyst is determined as follows: It can be less than 10 wt%, less than 5 wt%, or virtually zero (no catalytic activity), such as under the test methods disclosed in the examples.

The catalyst poisoning agent can include any material configured to bind to a transition metal (eg, platinum), such that the transition metal does not catalyze the aromatization reaction, and/or the transition metal is , Does not catalyze decomposition reactions. As disclosed herein, the mechanism by which the catalyst poison operates is not so limited. The catalyst poisoning agent is less than 10 wt%, less than 5 wt%, or virtually no in the sintering of platinum, platinum agglomeration, and/or pore plugging, and the aromatic yield of the deactivated catalyst. Materials can be included that cause any other suitable mechanism that causes zero (no catalytic activity), and additionally or alternatively, result in a deactivated catalyst that does not catalyze the decomposition reaction.

Although not a requirement, in order to facilitate use in a radial flow reactor during operation, the catalyst poison may be, for example, a gas over the entire temperature range of 200°C to 800°C, or 300°C to 700°C. Materials can be included that are gases over (or below) any range of temperature (eg, reforming temperature) disclosed herein, such as gas over a range of temperatures.

Exemplary and non-limiting examples of catalyst poisons include heavy hydrocarbons (eg, anthracene), sulfur-containing compounds (eg, thiophene such as H ₂ S, thiophene, benzothiophene, or dibenzothiophene, mercaptans). ), phosphorus-containing compounds (eg phosphates, phosphines), oxygen-containing compounds (eg acetaldehyde), bromine-containing compounds (eg brominated hydrocarbons such as dibromohexane), iodine-containing compounds (eg iodohexane etc.) Iodinated hydrocarbons), organometallic lead compounds (eg, tetraethyllead), organometallic arsenic compounds (eg, trimethylarsine), and the like, as well as combinations of two or more of these poisons. Other suitable catalyst poisons will be readily apparent to those of ordinary skill in the art in view of the present disclosure and are included herein.

Referring to FIG. 3, a representative plot of reactor temperature as a function of location in the reactor from the outer annulus to the center tube is illustrated when the catalyst closest to the outer annulus is spent. This indication is before the introduction of the catalyst poison. FIG. 4 shows a representative plot of reactor temperature as a function of location in the reactor from the outer annulus to the central tube when the catalyst closest to the outer annulus is deactivated with a catalyst poison. Illustrate. By poisoning (or completely deactivating) the spent catalyst in the outer reforming zone (closest to the outer annulus), more aromatization reaction can be achieved, further in the catalyst bed (closer to the central tube). , Inner reforming zone) resulting in minimally deactivated or minimal spent catalyst.

Thus, one beneficial and unexpected result of the reforming process utilizing catalyst poisoning agents disclosed herein is improved yield. For example, the yield of aromatic product in step (c) after addition of catalyst poisoning agent is the yield of aromatic product produced after step (a) and before step (b). Can be larger than. Similarly, the yield of the second aromatic product in step (D) after addition of the catalyst poisoning agent is the same as that of the first aromatic product produced after step (B) and before step (C). It can be higher than the yield of aromatic product.

Another beneficial and unexpected result of the reforming process utilizing catalyst poisoning agents disclosed herein is improved selectivity. For example, the selectivity of the aromatic product in step (c) after addition of the catalyst poisoning agent is determined by the selectivity of the aromatic product produced after step (a) and before step (b). Can be larger than. Similarly, the selectivity of the second aromatic product in step (D), after addition of the catalyst poison, is determined by the first aromatics produced after step (B) and before step (C). It can be greater than the selectivity of the aromatic product.

Although not limited thereto, the weight ratio (or volume ratio) of the amount of catalyst in the outer reforming zone to the amount of catalyst in the inner reforming zone is from about 10:1 to about 1:10, about. It can be within the range of 5:1 to about 1:5, or about 1:3 to about 3:1 (outer:inner). In some aspects, the outer reforming zone contains less catalyst than the inner reforming zone, and in these aspects, the outer:inner ratio is from about 1:1.2 to about 1:10, about 1. :1.5 to about 1:5, or about 1:2 to about 1:6, and the ratios can be on a weight basis or a volume basis. As will be appreciated by those skilled in the art, the relative size of the outer reforming zone and the inner reforming zone (or the relative amount of catalyst therein) is such that more catalyst in the catalyst bed is affected by the addition of catalyst poisons. It can change when inactivated or poisoned.

If desired, the method disclosed herein can further include an inert gas purging step after the catalyst poisoning step, the inert gas purging step introducing an inert gas stream into the radial flow reactor, And contacting the catalyst bed. The inert gas stream may comprise (or consist essentially of, or consist of) any suitable inert gas such as nitrogen or argon. Mixtures of two or more inert gases can be used.

The present invention is further illustrated by the following examples, which should in no way be construed as limiting the scope of the invention. Various other aspects, modifications, and equivalents thereof can be suggested to one skilled in the art after reading the description herein, without departing from the spirit of the invention or the scope of the appended claims. ..

Examples 1-2
In Examples 1-2, the fresh aromatization catalyst has a surface area of about 180 m ² /g, a pore volume of 0.2 cc/g, and a micropore volume of 0.06 cc/g, about 1% by weight. Pt/KL type zeolite containing platinum, 0.85 wt% Cl, and 0.75 wt% F (determined by XRF). The source of spent catalyst is fresh catalyst, but after partial deactivation after prolonged use in the aromatization reactor. With respect to Example 1, a sample of spent catalyst is taken from the section of the catalyst bed closest to the outer annulus of the reactor (near the outer particle barrier). For Example 2, a sample of spent catalyst is taken from the section of the catalyst bed closest to the central tube. Prior to use in these examples, each spent catalyst is subjected to a mild partial decoking step to remove unreacted hydrocarbons and light carbonaceous deposits from the catalyst.

Each used catalyst was crushed and sieved to 25-45 mesh, and 1 cc of the sieved catalyst was placed in a temperature-controlled furnace in a stainless steel reactor vessel with an outer diameter of 3/8 inch. To do. After reducing the catalyst under a stream of molecular hydrogen, the feed stream of aliphatic hydrocarbon and molecular hydrogen was subjected to a pressure of 100 psig (689 kPag), a H ₂ :hydrocarbon molar ratio of 1.3:1, and 12 hours ^−1. Is introduced into the reactor vessel at a liquid hourly space velocity (LHSV) of 1 to obtain catalyst performance data over time. The first 5-6 hours of the 40 hour test are conducted at 950°F (510°C) and the rest at 980°F (527°C). Aliphatic hydrocarbon feed contains convertible C ₇ kinds of convertible C ₆ or about 0.64 mole fraction and 0.21 mole fraction. The rest are aromatics, C ₈ ⁺ , and hyperbranched isomers, which are classified as non-convertible. The reactor effluent composition is analyzed by gas chromatography to determine total aromatics and aromatics selectivity.

The catalytic activity (aromatic yield) and catalyst selectivity data for the spent catalysts of Examples 1-2 are summarized in Figures 5 and 6, respectively. The spent catalyst of Example 1 (closest to the outer annulus) is significantly more than the spent catalyst of Example 2 (closest to the central tube), as evidenced by the lower aromatic yield in FIG. The activity is low. Similarly, FIG. 6 shows that the spent catalyst of Example 1 (closest to the outer annulus) is significantly less selective for aromatics than the spent catalyst of Example 2 (closest to the central tube). Make it clear.

Thus, Examples 1-2 show that the catalyst closest to the outer annulus is more "spent" and has lower activity and lower activity as compared to the catalyst closest to the central tube, which has excellent catalytic activity and selectivity. It demonstrates selectivity (lower aromatic yield, more decomposition reactions, lower aromatic selectivity).

Examples 3-4
In Examples 3-4, the fresh aromatization catalyst had a surface area of about 180 m ² /g, a pore volume of 0.2 cc/g, and a micropore volume of 0.06 cc/g, about 1 wt%. Pt/KL type zeolite containing platinum, 0.85 wt% Cl, and 0.75 wt% F (determined by XRF). The source of spent catalyst is fresh catalyst, but after partial deactivation after prolonged use in the aromatization reactor. Examples 3-4 are performed in much the same manner as Examples 1-2, but with the following differences. Example 3 uses a continuous fixed bed having a first zone containing 1 cc of spent catalyst and a second zone containing 1 cc of fresh catalyst (hydrocarbon feed before the second zone). First zone, i.e. contact with spent catalyst). Example 3 is a reference example, where the catalyst closest to the outer annulus has low activity and selectivity (eg, spent catalyst) and the catalyst closest to the central tube has excellent activity and selectivity (eg, Reactor with fresh catalyst or spent catalyst with less deactivation than the catalyst near the outer annulus). Example 4 uses a continuous fixed bed with a first zone containing 1 cc of deactivated (or poisoned) catalyst and a second zone containing 1 cc of fresh catalyst. The deactivated (or poisoned) catalyst is prepared by soaking a sample of the spent catalyst in a solution of K ₃ PO ₄ , thereby completely deactivating the catalyst. Performance data of the catalyst bed over time is taken at 950°F (510°C) for 40 hours of testing.

Catalytic activity (C 5 ₊ aromatic yield) and the catalyst selectivity data for the catalyst bed of Example 3-4, respectively, are summarized in FIGS. As evidenced by the higher aromatic yield in Figure 7, and unexpectedly, the catalyst bed of Example 4 (poisoned: new) is significantly more significant than the catalyst bed of Example 3 (spent: new). More active. Similarly, and surprisingly, FIG. 8 demonstrates that the catalyst bed of Example 4 is significantly more selective for aromatics than the catalyst bed of Example 3.

Thus, Examples 3-4 show that the aromatization reactor with the spent catalyst closest to the outer annulus has the catalyst closest to the outer annulus completely deactivated (or poisoned) aroma. It demonstrates the unexpected results of low aromatic yield, high decomposition reactions and low aromatic selectivity compared to the aromatization reactor. Thus, overall reactor performance with respect to aromatic yield and aromatic selectivity can be improved by selectively deactivating/poisoning the spent catalyst closest to the outer annulus.

The present invention has been described above with reference to a number of aspects and specific embodiments. Many variations will be apparent to those of skill in the art in light of the above detailed description. All such obvious variations are within the full intended scope of the appended claims. Other aspects of the invention include, but are not limited to, the following (aspects are described as “comprising”, but may alternatively be “consisting essentially of” or “consisting of”. Good).

Aspect 1. A reforming method,
(A) providing a radial flow reactor comprising a catalyst bed, the catalyst bed comprising an outer (first) reforming zone and an inner (second) reforming zone,
The outer reforming zone comprises a spent first aromatization catalyst comprising a first transition metal and a first catalyst support,
Providing an inner reforming zone comprising a second aromatization catalyst comprising a second transition metal and a second catalyst support;
(B) Introducing a catalyst poisoning agent (or catalyst deactivator) into the radial flow reactor, and (to partially or completely deactivate the portion of the spent first aromatization catalyst) ) Contacting at least a portion of the spent first aromatization catalyst in the outer reforming zone;
(C) introducing a hydrocarbon feed into a radial flow reactor containing the catalyst bed and contacting the hydrocarbon feed with the catalyst bed under reforming conditions to produce an aromatic product. Including a method.

Aspect 2. A reforming method,
(A) introducing a first hydrocarbon feed into a radial flow reactor containing a catalyst bed and contacting the first hydrocarbon feed with the catalyst bed under first reforming conditions to produce a first hydrocarbon feed; Producing an aromatic product of
The catalyst bed includes an outer (first) reforming zone and an inner (second) reforming zone,
The outer reforming zone comprises a first aromatization catalyst comprising a first transition metal and a first catalyst support,
Producing an inner reforming zone comprising a second aromatization catalyst comprising a second transition metal and a second catalyst support;
(B) performing step (A) for a period of time sufficient to form a spent first aromatization catalyst in the outer reforming zone;
(C) Introducing a catalyst poisoning agent (or catalyst deactivator) into the radial flow reactor and (to partially or completely deactivate a portion of the spent first aromatization catalyst) ) Contacting at least a portion of the spent first aromatization catalyst in the outer reforming zone;
(D) introducing a second hydrocarbon feed into the radial flow reactor containing the catalyst bed and contacting the second hydrocarbon feed with the catalyst bed under second reforming conditions to produce a second Producing an aromatic product of.

Aspect 3. Hydrocarbon feed, the first hydrocarbon feed, and a second hydrocarbon feed is independently comprise a non-aromatic hydrocarbon, wherein the C ₆ -C ₉ alkanes and / or cycloalkanes, or C ₆ -C including ₈ alkanes and / or cycloalkanes, method according to embodiment 1 or embodiment 2.

Aspect 4. The method of any one of the preceding aspects, wherein the hydrocarbon feed, the first hydrocarbon feed, and the second hydrocarbon feed independently comprise hexane, heptane, or a combination thereof. ..

Aspect 5. The method of any one of the preceding aspects, wherein the aromatic product, the first aromatic product, and the second aromatic product independently comprise benzene, toluene, or a combination thereof. ..

Aspect 6. The reforming conditions, the first reforming conditions, and the second reforming conditions are disclosed herein independently, for example, from about 350°C to about 600°C, or from about 400°C to about 600°C. The method according to any one of the preceding aspects, comprising a reforming temperature within any reforming temperature range.

Aspect 7. Any of the reforming conditions disclosed herein wherein the reforming conditions, the first reforming conditions, and the second reforming conditions are independently, for example, from about 20 psig (138 kPag) to about 100 psig (689 kPag). The method according to any one of the preceding aspects, comprising a reforming pressure within a pressure range.

Aspect 8. The method according to any one of the preceding aspects, wherein the first catalyst support and the second catalyst support independently comprise zeolite, amorphous inorganic oxide, or any combination thereof.

Aspect 9. The method of any one of the preceding aspects, wherein the first catalyst support and the second catalyst support independently comprise L-type zeolite, Y-type zeolite, mordenite, omega zeolite, and/or beta zeolite. ..

Aspect 10. The method according to any one of the preceding aspects, wherein the first catalyst support and the second catalyst support independently comprise potassium L-type zeolite or barium ion exchange L-type zeolite.

Aspect 11. The method of any one of the preceding aspects, wherein the first catalyst support and the second catalyst support independently comprise a binder comprising alumina, silica, mixed oxides thereof, or mixtures thereof. ..

Aspect 12. The first catalyst support and the second catalyst support (or respective catalysts) are independently based on any weight percent of binder disclosed herein, eg, the total weight of the support (or catalyst). The method of any one of the preceding aspects, comprising about 3 wt% to about 35 wt%, or about 5 wt% to about 30 wt% binder.

Aspect 13. The method according to any one of the preceding aspects, wherein the first catalyst support and the second catalyst support independently comprise silica bound K/L type zeolite.

Aspect 14. The method according to any one of the preceding aspects, wherein the first transition metal and the second transition metal independently comprise a Group 7-11 transition metal, or a Group 8-11 transition metal. ..

Aspect 15. The method according to any one of the preceding aspects, wherein the first transition metal and the second transition metal independently comprise platinum, rhenium, tin, iron, gold, or a combination thereof.

Aspect 16. The method according to any one of the preceding aspects, wherein the first transition metal and the second transition metal comprise platinum.

Aspect 17. The first aromatization catalyst, the second aromatization catalyst, and the used first aromatization catalyst are independently the transition metal (first or second) transition metal disclosed herein. According to any one of the preceding aspects comprising any weight percent range of transition metal, for example, from about 0.1% to about 10%, or from about 0.3% to about 5% by weight transition metal. Method.

Aspect 18. The first aromatization catalyst, the second aromatization catalyst, and the used first aromatization catalyst independently comprise any weight percent range of platinum disclosed herein, for example, The method according to any one of the preceding aspects, comprising about 0.1 wt% to about 10 wt%, or about 0.5 wt% to about 2 wt% platinum.

Aspect 19. Any one of the preceding embodiments wherein the first aromatization catalyst, the second aromatization catalyst, and the spent first aromatization catalyst independently comprise platinum on L-type zeolite. The method described in.

Aspect 20. Any of the preceding embodiments, wherein the first aromatization catalyst, the second aromatization catalyst, and the used first aromatization catalyst independently comprise platinum on K/L zeolite. The method according to one.

Aspect 21. In the preceding embodiment, the first aromatization catalyst, the second aromatization catalyst, and the used first aromatization catalyst independently comprise platinum on silica bound K/L zeolite. The method according to any one.

Aspect 22. The method of any one of the preceding aspects, wherein the first aromatization catalyst, the second aromatization catalyst, and the used first aromatization catalyst further comprise chlorine and fluorine.

Aspect 23. The first aromatization catalyst, the second aromatization catalyst, and the used first aromatization catalyst may independently comprise any amount of chlorine and/or any of the amounts disclosed herein. An amount of fluorine, such as about 0.01 wt% to about 5 wt%, or about 0.3 to about 1.3 wt% fluorine, and/or about 0.01 wt% to about 5 wt%, or about The method according to any one of the preceding embodiments comprising 0.3 to about 1.3% by weight chlorine.

Aspect 24. The first aromatization catalyst, the second aromatization catalyst, and the used first aromatization catalyst may independently comprise any of the fluorine:chlorine molar ratios disclosed herein, such as The method of any one of the preceding aspects, comprising about 0.2:1 to about 4:1.

Aspect 25. The weight ratio (or volume ratio) of catalyst in the outer reforming zone to the inner reforming zone is within any of the outer:inner ranges disclosed herein, for example, from about 10:1 to about 1:10. Or the method of any one of the preceding aspects, which is about 5:1 to about 1:5.

Aspect 26. The catalyst poisoning agent comprises a material configured to bind to a transition metal (eg, platinum), such that the transition metal does not catalyze an aromatization reaction and/or does not catalyze a decomposition reaction. The method according to any one of the aspects.

Aspect 27. The catalyst poisoning agent comprises a material that is a gas over any temperature range disclosed herein, such as a gas over a temperature range of 200°C to 800°C, or a gas over a temperature range of 300°C to 700°C. The method according to any one of the preceding aspects.

Aspect 28. The catalyst poison is a heavy hydrocarbon (eg, anthracene), a sulfur-containing compound (eg, H ₂ S, thiophene, mercaptan), a phosphorus-containing compound (eg, phosphate, phosphine), an oxygen-containing compound (eg, Acetaldehyde), bromine-containing compounds (eg, brominated hydrocarbons), iodine-containing compounds (eg, iodinated hydrocarbons), organometallic lead compounds (eg, tetraethyllead), organometallic arsenic compounds (eg, trimethylarsine), or The method according to any one of the preceding aspects, including any combination thereof.

Aspect 29. The catalyst poison can be within any of the ranges disclosed herein, such as about 0.01:1 to about 1:1, about 0.01:1 to about 0.5:1, or about 0.1. Any of the preceding embodiments, introduced in a molar ratio of moles of catalyst poisoning agent (in spent first aromatization catalyst) to moles of transition metal (from 1:1 to about 0.75:1). The method according to one.

Aspect 30. The amount of carbon on the spent first aromatization catalyst is within the range of any of the weight percentages of carbon disclosed herein, such as from about 1 to 10% by weight, or from about 1.5 to about. The method according to any one of the preceding embodiments, wherein 7% by weight of carbon.

Aspect 31. The amount of carbon on the first aromatization catalyst and the second aromatization catalyst may independently be a weight percentage within any range of carbon disclosed herein, eg, about 0.9 weight. %, less than about 0.5% by weight, about 0.01% by weight to about 0.9% by weight, about 0.01% by weight to about 0.5% by weight, or about 0.02% by weight to about 0.0% by weight. The method according to any one of the preceding embodiments, which is 5% by weight carbon.

Aspect 32. The method of any one of the preceding aspects, wherein the temperature of the hydrocarbon feed, the first hydrocarbon feed, and the second hydrocarbon feed decreases from the outer reforming zone to the inner reforming zone. Method.

Aspect 33. In any one of the preceding embodiments, the activity (eg, aromatic yield) of the second aromatization catalyst is greater than the activity of the used first aromatization catalyst under the same test conditions. The method described.

Aspect 34. A method according to any one of the preceding aspects, wherein the aromatic selectivity of the second aromatization catalyst is greater than the selectivity of the used first aromatization catalyst under the same test conditions.

Aspect 35. The aromatic yield of the used first aromatization catalyst after contact with the catalyst poisoning agent is less than 10% by weight, for example less than 5% by weight, or virtually zero (no catalytic activity), The method according to any one of the preceding aspects.

Aspect 36. The yield of aromatic product in step (c) is greater than the yield of aromatic product produced after step (a) and before step (b), and in the second step in step (D). Aspect according to any one of the preceding aspects, wherein the yield of aromatic product is greater than the yield of the first aromatic product produced after step (B) and before step (C). the method of.

Aspect 37. The aromatic selectivity of the aromatic product in step (c) is greater than the aromatic selectivity of the aromatic product produced after step (a) and before step (b), and step (D) The aromatic selectivity of the second aromatic product in is greater than the aromatic selectivity of the first aromatic product produced after step (B) and before step (C). The method according to any one of the aspects.

Aspect 38. The method further comprises an inert gas purging step after the catalyst poisoning step, the inert gas purging step including introducing an inert gas stream into the radial flow reactor and contacting the catalyst bed with the inert gas stream. The method according to any one of the preceding aspects, wherein comprises (or consists essentially of, or consists of) any inert gas disclosed herein, such as nitrogen.

Aspect 39. An aromatization reactor vessel,
(I) a reactor wall,
(Ii) a catalyst bed positioned within the reactor vessel,
(Iii) an outer annulus positioned between the reactor wall and the outer particle barrier, the outer particle barrier and the outer annulus surrounding the catalyst bed;
(Iv) a reactor inlet for the feed stream,
(V) a reactor outlet connected to the central tube, the central tube being positioned within the reactor vessel and surrounded by the catalyst bed;
The catalyst bed comprises an outer (first) reforming zone and an inner (second) reforming zone, the outer reforming zone comprising a deactivated first transition metal and a first catalyst support. Including a first aromatization catalyst, the inner reforming zone including a second aromatization catalyst including a second transition metal and a second catalyst support;
A flow path for the feed stream begins at the reactor inlet, continues to the outer annulus, through the outer particle barrier, the outer reforming zone, and the inner reforming zone, to the central tube, and to the reactor outlet. , Aromatization reactor vessel.

Aspect 40. 40. The reactor vessel of aspect 39, wherein the reactor vessel comprises stainless steel.

Aspect 41. 41. The reactor vessel of embodiment 39 or 40, wherein the outer annulus includes flow-influencing elements (eg, scallops adjacent to the reactor wall) in the flow path to facilitate flow through the catalyst bed. ..

Aspect 42. The reactor vessel is, for example, at least 20 psig (138 kPag), at least 30 psig (207 kPag), or about 20 psig (138 kPag) to about 100 psig (689 kPag), any suitable range disclosed herein, or any range. 42. A reactor vessel according to any one of aspects 39-41 configured for an operating pressure within.

Aspect 43. A reactor vessel according to any one of aspects 39-42, wherein the central tube and the catalyst bed are concentrically positioned.

Aspect 44. A reactor vessel according to any one of aspects 39-43, wherein the central tube comprises a screen or mesh section within the reactor vessel.

Aspect 45. Any of aspects 39-44, wherein the central tube comprises a coating/layer comprising any suitable metal disclosed herein or any metal (eg, tin) that provides resistance to carburization and metal dusting. The reactor container according to one.

Aspect 46. Any of aspects 39-45, wherein the reactor vessel comprises a coating/layer comprising any suitable metal disclosed herein or any metal (eg, tin) that provides resistance to carburization and metal dusting. The reactor container according to one.

Aspect 47. 47. A reactor vessel according to any one of aspects 39-46, wherein the reactor vessel is configured to reduce the temperature from the outer annulus to the central tube (or from the outer reforming zone to the inner reforming zone). ..

Aspect 48. 48. A reactor vessel according to any one of aspects 39-47, wherein the reactor vessel is configured as a radial flow reactor.

Aspect 49. The reactor of any one of aspects 39-48, wherein the reactor vessel is configured for catalytic conversion of non-aromatic hydrocarbons to aromatic hydrocarbons (eg, benzene, toluene, or xylene). container.

Aspect 50. 50. The reactor vessel of any one of aspects 39-49, wherein the reactor vessel further comprises a central tube and a top cover plate positioned on top of the catalyst bed.

Aspect 51. 51. The reactor vessel of any one of aspects 39-50, wherein the reactor vessel further comprises an integrated heat exchange system around at least a portion of the reactor vessel to control the temperature within the reactor vessel.

Aspect 52. 52. The reactor vessel of any one of aspects 39-51, wherein the first catalyst support and the second catalyst support independently comprise zeolite, amorphous inorganic oxide, or any combination thereof.

Aspect 53. 53. The embodiment of any one of aspects 39-52, wherein the first catalyst support and the second catalyst support independently comprise L-type zeolite, Y-type zeolite, mordenite, omega zeolite, and/or beta zeolite. Reactor vessel.

Aspect 54. 54. The reactor vessel of any one of aspects 39-53, wherein the first catalyst support and the second catalyst support independently comprise potassium L-type zeolite or barium ion exchange L-type zeolite.

Aspect 55. 55. The embodiment of any one of aspects 39-54, wherein the first catalyst support and the second catalyst support independently comprise a binder comprising alumina, silica, mixed oxides thereof, or mixtures thereof. Reactor vessel.

Aspect 56. 56. The reactor vessel of any one of aspects 39-55, wherein the first catalyst support and the second catalyst support independently comprise silica bound K/L type zeolite.

Aspect 57. 57. The any one of aspects 39-56, wherein the first transition metal and the second transition metal independently comprise a Group 7-11 transition metal, or a Group 8-11 transition metal. Reactor vessel.

Aspect 58. 58. The reactor vessel of any one of aspects 39-57, wherein the first transition metal and the second transition metal independently comprise platinum, rhenium, tin, iron, gold, or a combination thereof.

Aspect 59. 59. The reactor vessel of any one of aspects 39-58, wherein the first transition metal and the second transition metal comprise platinum.

Aspect 60. 60. The reactor vessel of any one of aspects 39-59, wherein the deactivated first aromatization catalyst and second aromatization catalyst independently comprise platinum in the form of L-type zeolite. ..

Aspect 61. 61. The reaction according to any one of aspects 39-60, wherein the deactivated first aromatization catalyst and second aromatization catalyst independently comprise platinum on K/L type zeolite. Vessel.

Aspect 62. The embodiment of any one of aspects 39-61, wherein the deactivated first aromatization catalyst and second aromatization catalyst independently comprise platinum on silica-bound K/L-type zeolite. Reactor vessel.

Aspect 63. 63. The reactor vessel of any one of aspects 39-62, wherein the deactivated first aromatization catalyst and second aromatization catalyst further comprise chlorine and fluorine.

Aspect 64. The weight ratio (or volume ratio) of catalyst to outer reforming zone in the outer reforming zone is within any of the outer:inner ranges disclosed herein, for example, from about 10:1 to about 1:10, or The reactor vessel according to any one of aspects 39-63, which is about 5:1 to about 1:5.

Aspect 65. Aspect any one of aspects 39-64, wherein the deactivated first aromatization catalyst is configured not to catalyze an aromatization reaction and/or not to catalyze a decomposition reaction. The reactor vessel described.

Aspect 66. The amount of carbon on the deactivated first aromatization catalyst can be a weight percentage within any range of carbon disclosed herein, such as about 1 to 10 wt%, or about 1.5. A reactor vessel according to any one of aspects 39-65, wherein the reactor vessel is about 7 wt% carbon.

Aspect 67. The amount of carbon on the second aromatization catalyst is a weight percentage within any range of carbon disclosed herein, such as less than about 0.9 wt%, less than about 0.5 wt%, Aspects 39-about 0.01% to about 0.9% by weight, about 0.01% to about 0.5% by weight, or about 0.02% to about 0.5% by weight carbon. 66. The reactor vessel according to any one of 66.

Aspect 68. Any of embodiments 39-67, wherein the aromatic yield of the deactivated first aromatization catalyst is less than 10% by weight, for example less than 5% by weight, or virtually zero (no catalytic activity). 1. The reactor container according to one.

Aspect 69. The reactor vessel is larger than that obtained using the spent first aromatization catalyst instead of the deactivated first aromatization catalyst in the outer reforming zone. 69. The reactor vessel of any one of aspects 39-68 configured for aromatic yield at the outlet.

Aspect 70. The reactor vessel is larger than that obtained using the spent first aromatization catalyst instead of the deactivated first aromatization catalyst in the outer reforming zone. 70. A reactor vessel according to any one of aspects 39-69 configured for aromatic selectivity at the outlet.

Aspect 71. An aromatization reactor system comprising one or more aromatization reactor vessels, at least one of which is the reactor vessel of any one of aspects 39-70.

Aspect 72. The system comprises any suitable number of reactor vessels in series or any number of reactor vessels in series disclosed herein, eg, 2-8 vessels in series, or 6 vessels in series. The system according to aspect 71.

Aspect 73. The system further includes a furnace in front of each reactor vessel, each furnace feeding stream (or reactor effluent of the previous reactor vessel) to a reactor vessel operating temperature of about 350°C to about 600°C. The system of aspect 72, which is independently configured to heat.

Claims (17)

A reforming method,
(A) introducing a first hydrocarbon feed into a radial flow reactor containing a catalyst bed and contacting the first hydrocarbon feed with the catalyst bed under first reforming conditions; Producing a first aromatic product, the method comprising:
The catalyst bed includes an outer reforming zone and an inner reforming zone,
The outer reforming zone comprises a first aromatization catalyst comprising a first transition metal and a first catalyst support,
Producing the inner reforming zone comprises a second aromatization catalyst comprising a second transition metal and a second catalyst support;
(B) performing step (A) for a period of time sufficient to form a spent first aromatization catalyst in the outer reforming zone;
(C) Introducing a catalyst poisoning agent into the radial flow reactor and contacting with at least a portion of the spent first aromatization catalyst in the outer reforming zone for poisoning aromatization. Forming a catalyst,
(D) introducing a second hydrocarbon feed into the radial flow reactor containing the catalyst bed and contacting the second hydrocarbon feed with the catalyst bed under second reforming conditions. To produce a second aromatic product,
The spent first aromatization catalyst contains from about 1 wt% to about 10 wt% carbon;
The aromatic yield of the poisoned aromatization catalyst is less than 10% by weight,
The catalyst poisoning agent includes heavy hydrocarbons, sulfur-containing compounds, phosphorus-containing compounds, oxygen-containing compounds, bromine-containing compounds, iodine-containing compounds, organometallic lead compounds, organometallic arsenic compounds, or any combination thereof. See
The first aromatization catalyst comprises about 0.3% to about 5% by weight of the first transition metal;
The second aromatization catalyst comprises about 0.3% to about 5% by weight of the second transition metal;
The first transition metal and the second transition metal include platinum,
The first catalyst carrier and the second catalyst carrier include K/L type zeolite and a binder containing alumina, silica, a mixed oxide thereof, or a mixture thereof,
The first aromatization catalyst and the second aromatization catalyst further including chlorine and fluorine, methods. The first aromatic product and the second aromatic product independently comprise benzene, toluene, or a combination thereof,
The method of claim 1, wherein the first reforming condition and the second reforming condition independently comprise a reforming temperature in the range of about 350°C to about 600°C. The method of claim 1, wherein the weight ratio of catalyst in the outer reforming zone to the inner reforming zone is in the range of about 1:1.5 to about 1:5. The first aromatization catalyst, and the second aromatization catalyst are each independently comprises from about 0.5% to about 2 wt% platinum The method of claim 1. The catalyst poisoning agent is from about 0.1:1 to about 0. 0, based on moles of the catalyst poisoning agent relative to moles of the first transition metal in the spent first aromatization catalyst. The method of claim 1, wherein the method is introduced at a molar ratio within the range of 75:1. The first transition metal and the second transition metal include platinum,
The first catalyst carrier and the second catalyst carrier include K/L-type zeolite and a binder containing alumina, silica, a mixed oxide thereof, or a mixture thereof, and
6. The method of claim 5 , wherein the used first aromatization catalyst and the second aromatization catalyst further comprise chlorine and fluorine. The aromatic yield of the second aromatization catalyst is greater than the yield of the used first aromatization catalyst under the same test conditions,
The method of claim 1, wherein the aromatic selectivity of the second aromatization catalyst is greater than the selectivity of the spent first aromatization catalyst under the same test conditions. The aromatic yield of the second aromatic product in step (D) is greater than the yield of the first aromatic product produced after step (B) and before step (C). The method of claim 1, wherein: The aromatic selectivity of the second aromatic product in step (D) is such that the aromatic selectivity of the first aromatic product produced after step (B) and before step (C). The method of claim 1, wherein the method is greater than sex. A reforming method,
(A) providing a radial flow reactor comprising a catalyst bed, said catalyst bed comprising an outer reforming zone and an inner reforming zone,
The outer reforming zone comprises a spent first aromatization catalyst comprising a first transition metal and a first catalyst support,
Providing the inner reforming zone comprises a second aromatization catalyst comprising a second transition metal and a second catalyst support;
(B) introducing a catalyst poisoning agent into the radial flow reactor and contacting with at least a portion of the spent first aromatization catalyst in the outer reforming zone to poisoned aromatization. Forming a catalyst,
(C) introducing a hydrocarbon feed into the radial flow reactor containing the catalyst bed and contacting the hydrocarbon feed with the catalyst bed under reforming conditions to produce an aromatic product. Including
The spent first aromatization catalyst contains from about 1 wt% to about 10 wt% carbon;
The aromatic yield of the poisoned aromatization catalyst is less than 10% by weight,
The catalyst poisoning agent includes heavy hydrocarbons, sulfur-containing compounds, phosphorus-containing compounds, oxygen-containing compounds, bromine-containing compounds, iodine-containing compounds, organometallic lead compounds, organometallic arsenic compounds, or any combination thereof. See
The used first aromatization catalyst comprises from about 0.3% to about 5% by weight of the first transition metal;
The second aromatization catalyst comprises about 0.3% to about 5% by weight of the second transition metal;
The first transition metal and the second transition metal include platinum,
The first catalyst carrier and the second catalyst carrier include K/L type zeolite and a binder containing alumina, silica, a mixed oxide thereof, or a mixture thereof;
The spent first aromatization catalyst and the second aromatization catalyst further including chlorine and fluorine, methods. The aromatic yield of the aromatic product in step (c) is greater than the yield of aromatic product produced after step (a) and before step (b),
The aromatic selectivity of the aromatic product in step (c) is greater than the aromatic selectivity of the aromatic product produced after step (a) and before step (b). 10. The method according to 10 . The used first aromatization catalyst and the second aromatization catalyst each independently contain from about 0.3% to about 5% by weight of platinum; and
The method of claim 11 , wherein the aromatic product comprises benzene, toluene, or a combination thereof. 13. The method of claim 12 , wherein the used first aromatization catalyst contains from about 1.5 wt% to about 7 wt% carbon. A reforming method,
(A) introducing a first hydrocarbon feed into a radial flow reactor containing a catalyst bed and contacting the first hydrocarbon feed with the catalyst bed under first reforming conditions, Producing a first aromatic product, the method comprising:
The catalyst bed includes an outer reforming zone and an inner reforming zone,
The outer reforming zone comprises a first aromatization catalyst comprising a first transition metal and a first catalyst support,
Producing the inner reforming zone comprises a second aromatization catalyst comprising a second transition metal and a second catalyst support;
(B) performing step (A) for a period of time sufficient to form a spent first aromatization catalyst in the outer reforming zone;
(C) Introducing a catalyst poisoning agent into the radial flow reactor and contacting with at least a portion of the spent first aromatization catalyst in the outer reforming zone for poisoning aromatization. Forming a catalyst,
(D) introducing a second hydrocarbon feed into the radial flow reactor containing the catalyst bed and contacting the second hydrocarbon feed with the catalyst bed under second reforming conditions. To produce a second aromatic product,
The spent first aromatization catalyst contains from about 1 wt% to about 10 wt% carbon;
The aromatic yield of the poisoned aromatization catalyst is less than 10% by weight,
The catalyst poisoning agent includes heavy hydrocarbons, sulfur-containing compounds, phosphorus-containing compounds, oxygen-containing compounds, bromine-containing compounds, iodine-containing compounds, organometallic lead compounds, organometallic arsenic compounds, or any combination thereof. See
The first aromatization catalyst comprises about 0.3% to about 5% by weight of the first transition metal;
The second aromatization catalyst comprises about 0.3% to about 5% by weight of the second transition metal;
The first transition metal and the second transition metal include platinum,
The first catalyst carrier and the second catalyst carrier include K/L type zeolite and a binder containing alumina, silica, a mixed oxide thereof, or a mixture thereof,
The first aromatization catalyst and the second aromatization catalyst further seen including chlorine and fluorine,
The aromatic yield of the second aromatic product in step (D) is higher than the yield of the first aromatic product produced after step (B) and before step (C). Big and
The aromatic selectivity of the second aromatic product in step (D) is the aromatic selectivity of the first aromatic product produced after step (B) and before step (C). Greater than,
The above modification method. 15. The method of claim 14 , wherein the first aromatization catalyst and the second aromatization catalyst each independently comprise from about 0.5 wt% to about 2 wt% platinum. The first aromatic product and the second aromatic product each independently include benzene, toluene, or a combination thereof; and
16. The method of claim 15 , wherein the first catalyst support and the second catalyst support comprise silica bound K/L type zeolite. The weight ratio of catalyst in the outer reforming zone to the inner reforming zone is in the range of about 1:1.5 to about 1:5, and
The catalyst poisoning agent is about 0.1:1 to 1 based on the ratio of moles of the catalyst poisoning agent to moles of the first transition metal in the used first aromatization catalyst. 15. The method of claim 14 introduced at a molar ratio within the range of about 0.75:1.